JP2020132593A - Method for producing 1,1,2-trifluoroethane (HFC-143) - Google Patents

Abstract

To provide a method for producing HFC-143, which is inexpensive and more efficient than the conventional method.SOLUTION: A method for producing 1,1,2-trifluoroethane (HFC-143), including a step of contacting at least one chlorine-containing compound selected from the group consisting of 1,1,2-trichloroethane (HCC-140), 1,2-dichloro-1-fluoroethane (HCFC-141), 1,1-dichloro-2-fluoroethane (HCFC-141a), (E,Z)-1,2-dichloroethylene (HCO-1130(E,Z)) and (E,Z)-1-chloro-2-fluoroethylene (HCFO-1131(E,Z)) with hydrogen fluoride in order to perform one or more fluorination reaction, and a reaction gas containing HFC-143, hydrogen chloride and hydrogen fluoride is obtained.SELECTED DRAWING: None

Description

The present disclosure relates to a method for producing 1,1,2-trifluoroethane (HFC-143).

Fluoroethane represented by 1,1,2-trifluoroethane (CHF ₂ CH ₂ F; hereinafter referred to as "HFC-143") is known as a raw material for producing various refrigerants. For example, HFC-143 is known as a raw material for 1,2-difluoroethylene (HFO-1132).

As a method for producing fluoroethane such as HFC-143, various methods have been conventionally proposed. For example, Patent Document 1 proposes a technique for producing HFC-143 by a hydrogenation reaction of chlorotrifluoroethylene (CTFE) or the like in the presence of a hydrogenation catalyst. Further, Patent Document 2 discloses a technique for producing 2-chloro-1,1-difluoroethane (HCFC-142) from 1,1,2-trichloroethane (HCC-140), and HFC as a by-product. It is described that -143 is mixed in a trace amount.

Japanese Unexamined Patent Publication No. 1-287044 International Publication No. 2015/082812

However, when HFC-143 is produced by the method disclosed in Patent Document 1, there is a problem that the raw material CTFE is expensive. Further, Patent Document 2 discloses a method for producing HCFC-142 as well, and the selectivity of HFC-143 mixed in a trace amount as a by-product in an organic substance is as small as 1.9%.

The present disclosure has been made in view of the above problems, and an object of the present disclosure is to provide a method for producing the target product, HFC-143, at low cost and more efficiently than the conventional method.

The present disclosure includes, for example, the inventions described in the following sections.
A method for producing 1,1,1,2-trifluoroethane (HFC-143).
1,1,2-Trichloroethane (HCC-140), 1,2-dichloro-1-fluoroethane (HCFC-141), 1,1-dichloro-2-fluoroethane (HCFC-141a), (E, Z) At least one selected from the group consisting of -1,2-dichloroethylene (HCO-1130 (E, Z)) and (E, Z) -1-chloro-2-fluoroethylene (HCFO-1131 (E, Z)). A method for producing HFC-143, which comprises a step of carrying out one or more fluorination reactions by contacting the chlorine-containing compound of HFC with hydrogen fluoride to obtain a reaction gas containing HFC-143, hydrogen chloride and hydrogen fluoride.
2. 2. Item 2. The production method according to Item 1, wherein the fluorination reaction is carried out under a pressure condition of 0 to 2 MPaG.
3. 3. Item 2. The production method according to Item 1 or 2, wherein the fluorination reaction is carried out in the gas phase in the presence of a catalyst.
4. Item 3. The production method according to Item 3, wherein the fluorination reaction is carried out under temperature conditions of 150 to 600 ° C.
5. Item 3. The production method according to Item 3 or 4, wherein the contact time W / Fo between the chlorine-containing compound and the hydrogen fluoride in the fluorination reaction is 0.1 to 100 g · sec / cc.
6. The production method according to any one of Items 1 to 5, wherein the molar ratio of hydrogen fluoride to the chlorine-containing compound in the fluorination reaction is 20 or more.
7. The production method according to any one of Items 1 to 5, wherein the molar ratio of hydrogen fluoride to the chlorine-containing compound in the fluorination reaction exceeds 40.
8. The production method according to any one of Items 3 to 7, wherein the catalyst is at least a chromium-based catalyst.
9. Item 2. The production method according to Item 1 or 2, wherein the fluorination reaction is carried out in a liquid phase in the presence of a catalyst.
10. Item 9. The production method according to Item 9, wherein the catalyst is at least partly an antimony-based catalyst.
11. 1. It has a step of subjecting 1,1,2-trifluoroethane (HFC-143) contained in the reaction gas obtained by the production method according to any one of Items 1 to 10 to a hydrogen fluoride reaction. A method for producing 2-difluoroethylene (HFO-1132).

According to the method for producing HFC-143 of the present disclosure, it is possible to provide an inexpensive and more efficient method for producing HFC-143 than the conventional method.

The method for producing HFC-143 of the present disclosure is 1,1,2-trichloroethane (HCC-140), 1,2-dichloro-1-fluoroethane (HCFC-141), 1,1-dichloro-2-fluoroethane. (HCFC-141a), (E, Z) -1,2-dichloroethylene (HCO-1130 (E, Z)) and (E, Z) -1-chloro-2-fluoroethylene (HCFO-1131 (E, Z)) )) A reaction gas containing HFC-143, hydrogen chloride and hydrogen fluoride, which comprises a step of carrying out one or more fluorination reactions by contacting at least one chlorine-containing compound selected from the group consisting of hydrogen fluoride with hydrogen fluoride. It is characterized by obtaining.

According to the method for producing HFC-143 of the present disclosure having the above-mentioned characteristics, it is possible to provide an inexpensive and more efficient method for producing HFC-143 than the conventional method.

In the production method of the present disclosure, the raw material compound contains at least one selected from the group consisting of HCC-140, HCFC-141, HCFC-141a, HCO-1130 (E, Z) and HCFO-1131 (E, Z). Use chlorine compounds. The (E, Z) means that the E-form and / or the Z-form are included. Since all of these chlorine-containing compounds are available at a lower cost than CTFE, the cost of producing HFC-143 can be reduced. Among these chlorine-containing compounds, at least one of HCC-140 and HCO-1130 (E, Z) is preferable from the viewpoint of raw material cost.

The production method of the present disclosure includes a step of carrying out one or more fluorination reactions by contacting the chlorine-containing compound with hydrogen fluoride to obtain a reaction gas containing HFC-143, hydrogen chloride and hydrogen fluoride. It is characterized by.

The fluorination reaction with hydrogen fluoride may be a gas phase reaction or a liquid phase reaction. Further, the number of fluorination reactions required to obtain HFC-143 may be one or two or more depending on the chlorine-containing compound used.

In the case of a gas phase reaction, it is sufficient that the chlorine-containing compound and hydrogen fluoride can come into contact with each other in a gaseous state in the reaction temperature region described later, and the chlorine-containing compound may be in a liquid state when the chlorine-containing compound is supplied.

For example, when the chlorine-containing compound is liquid at normal temperature and pressure, the chlorine-containing compound is vaporized using a vaporizer, passed through a preheating region, and supplied to a mixed region in contact with hydrogen fluoride. Allows the reaction to take place in the vapor phase state. Alternatively, the chlorine-containing compound may be supplied to the reactor in a liquid state and vaporized to react when it reaches the reaction region with hydrogen fluoride.

Further, as hydrogen fluoride, it is preferable to use anhydrous hydrogen fluoride because it can suppress corrosion of the reactor and deterioration of the catalyst.

The method for vaporizing the chlorine-containing compound in the reaction region is not particularly limited, and a known method can be widely adopted. For example, the temperature distribution in the reaction tube can be adjusted by filling the reaction tube with a material that has good thermal conductivity such as nickel beads and hasteroi pieces, has no catalytic activity in the fluorination reaction, and is stable against hydrogen fluoride. It may be made uniform, heated to a temperature higher than the vaporization temperature of the chlorine-containing compound, and the chlorine-containing compound in a liquid state may be supplied to vaporize the compound to bring it into a vapor phase state.

The method of supplying hydrogen fluoride to the reactor is not particularly limited, and examples thereof include a method of supplying hydrogen fluoride to the reactor in a vapor phase state together with a chlorine-containing compound. Regarding the supply amount of hydrogen fluoride, the molar ratio of hydrogen fluoride to the chlorine-containing compound (1 mol) is preferably 20 or more, preferably 30 or more, and more preferably 40 or more (particularly over 40). The upper limit of the molar ratio is not limited, but is preferably about 60 from the viewpoint of energy cost and productivity.

By setting the molar ratio, both the conversion rate of the chlorine-containing compound and the selectivity of HFC-143 can be maintained within an efficient (good) range as compared with the conventional method. In particular, when hydrogen fluoride is supplied in an amount of 40 mol or more (particularly more than 40 mol) with respect to 1 mol of the chlorine-containing compound, the selectivity of HFC-143 can be made extremely high.

In the present specification, the "conversion rate" is the total amount of compounds other than the above contained in the outflow gas (= reaction gas) from the reactor outlet with respect to the molar amount of the chlorine-containing compound supplied to the reactor. It shall mean the ratio of molar quantity (mol%).

Further, in the present specification, the "selectivity" means the target compound (HFC-) contained in the effluent gas with respect to the total molar amount of the compounds other than the above contained in the effluent gas (= reaction gas) from the reactor outlet. It shall mean the ratio (mol%) of the molar amount of 143).

In the vapor phase fluorination reaction, the chlorine-containing compound as a raw material compound may be supplied to the reactor as it is, or may be diluted with an inert gas such as nitrogen, helium or argon and supplied.

When the fluorination reaction is carried out in the gas phase in the presence of a catalyst, a known gas phase fluorination catalyst can be widely adopted, and there is no particular limitation. Examples include oxides of chromium, aluminum, cobalt, manganese, nickel, and iron, hydroxides, halides, halogen oxides, inorganic salts and mixtures thereof. Among these, in order to improve the conversion rate of the chlorine-containing compound, CrO ₂ , Cr ₂ O ₃ , FeCl ₃ / C, Cr ₂ O ₃ / Al ₂ O ₃ , Cr ₂ O ₃ / AlF ₃ , Cr ₂ O It is preferable to use a chromium-based catalyst such as ₃ / C and CoCl ₂ / Cr ₂ O ₃ . Chromium oxide / aluminum oxide catalysts are those described in US Pat. No. 5,155,082, that is, chromium oxide / aluminum oxide catalysts (eg, Cr ₂ O ₃ / Al ₂ O ₃ ), and cobalt. A composite of a halide of nickel, manganese, rhodium, and ruthenium can be preferably used. That is, in the case of a gas phase reaction, it is preferable that at least a part of the catalyst is a chromium-based catalyst.

As the catalyst metal, a partially or completely crystallized one may be used, an amorphous metal may be used, and the crystallinity can be appropriately selected. For example, chromium oxide is commercially available in various particle sizes. Further, in order to control the particle size and crystallinity, it may be prepared by precipitating chromium hydroxide from chromium nitrate and ammonia and then firing the mixture. The catalyst may be used alone or a mixture thereof. Further, as the carrier, various activated carbons, magnesium oxide, zirconia oxide, alumina and the like can be used. These catalysts may be subjected to a fluorination treatment using hydrofluoric acid anhydride, a fluorine-containing compound or the like before being used in the fluorination reaction, and are particularly preferably hydrofluoric acid treatment.

The form of the reactor to be used is not particularly limited, and a known reactor can be widely used. For example, a tube-type flow reactor filled with a catalyst can be used. When the reaction is carried out in the absence of a catalyst, for example, an adiabatic reactor in an empty tower, a porous or non-porous metal for improving the gas phase mixed state of hydrogen fluoride and a starting material, or An adiabatic reactor filled with a medium or the like may be used. In addition, it is also preferable to use a multi-tube reactor or the like in which heat is removed and / or the temperature distribution in the reactor is made uniform by using a heat medium.

When using a reactor with an empty tower, in a method of improving heat transfer efficiency by using a reaction tube having a small inner diameter, for example, the relationship between the flow rate of a chlorine-containing compound and the inner diameter of the reaction tube has a large linear velocity and heat transfer. It is preferable that the area is large.

The reaction temperature in the vapor phase fluorination reaction is preferably 150 to 600 ° C., more preferably 200 to 500 ° C., and even more preferably 230 to 400 ° C. as the temperature in the reactor. By setting the reaction temperature to 200 ° C. or higher, the selectivity of the target product can be improved. Further, by setting the reaction temperature to 600 ° C. or lower, the risk of carbides being generated by the reaction and the carbides adhering to and / or accumulating on the reaction tube wall and the filler and gradually clogging the reactor is reduced. can do. However, if such a risk is assumed, the carbides remaining in the reaction tube should be burned and removed by accommodating oxygen in the reaction system or by temporarily stopping the reaction and allowing oxygen or air to flow. Can be done.

The reaction pressure in the vapor phase fluorination reaction is not particularly limited as long as the chlorine-containing compound and hydrogen fluoride can exist in the vapor phase state, and may be under normal pressure, pressure, or reduced pressure. .. For example, it can be carried out under reduced pressure or atmospheric pressure (0 MPaG), and can also be carried out under pressure to the extent that the raw material does not become liquid. Usually, the pressure condition is preferably in the range of 0 to 2 MPaG, more preferably in the range of 0 to 1 MPaG.

The reaction time in the vapor phase fluorination reaction is not particularly limited, but usually, the catalyst charge amount W with respect to the total flow rate Fo (flow rate at 0 ° C. and 0.0 MPaG: cc / sec) of the raw material gas flowing through the reaction system. The ratio of (g): The contact time represented by W / Fo may be about 0.1 to 100 g · sec / cc, preferably about 5 to 50 g · sec / cc. The total flow rate of the raw material gas in this case is the total flow rate of the chlorine-containing compound and hydrogen fluoride used as the raw material, plus the flow rates of the inert gas and oxygen when used. is there.

On the other hand, when the fluorination reaction is carried out in a liquid phase in the presence of a catalyst, a known liquid phase fluorination catalyst can be widely adopted, and there is no particular limitation. Specifically, one or more selected from the group consisting of Lewis acid, transition metal halide, transition metal oxide, metal halide of group IVb, and metal halide of group Vb can be used.

More specifically, from the group consisting of antimonate halide, tin halide, tantalum halide, titanium halide, niobium halide, molybdenum halide, iron halide, chromium halide, and chromium fluoride oxide. One or more selected species can be used.

More specifically, SbCl ₅ , SbCl ₃ , SbF ₅ , SnCl ₄ , TaCl ₅ , TiCl ₄ , NbCl ₅ , MoCl ₆ , FeCl ₃ , and SbCl _(5-y ) prepared from chloride salts and hydrogen fluoride. _{) F y, SbCl (3-} y) F y, SnCl (4-y) F y, TaCl (5-y) Fy, TiCl (4-y) Fy, NbCl (5-y) Fy, MoCl (6- _{y) F y, FeCl (3} -y) F y ( where, y is 0.1 or more as a lower limit, the upper limit is less valences of the respective elements.) catalysts are preferred, such as. One of these catalysts may be used alone, or a plurality of types may be mixed and used. Of these, at least a part is preferably an antimony catalyst, and antimony trichloride is particularly preferable.

When these catalysts become inactive, they can be easily regenerated by known methods. As a method for regenerating the catalyst, a method of bringing chlorine into contact with the catalyst can be adopted. For example, about 0.15 to 25 g / hr of chlorine can be added to the liquid phase reaction per 100 g of the liquid phase fluorinated catalyst.

The reaction temperature in the liquid phase fluorination reaction is preferably 50 to 200 ° C., more preferably 80 to 150 ° C. as the temperature in the reaction system. By setting the reaction temperature to 80 ° C. or higher, the selectivity and productivity of the target product can be improved. The pressure in the liquid phase fluorination reaction is preferably in the range of 0 to 2 MPaG, more preferably 0 to 1 MPaG, as in the case of the gas phase reaction.

As the reactor, known reactors can be widely used for both the fluorination reaction in the gas phase and the fluorination reaction in the liquid phase, and there is no particular limitation. Specifically, it is preferable to use a material composed of a material resistant to the corrosive action of hydrogen fluoride, such as Hastelloy, INCONEL, MONEL, and INCOLLY.

After obtaining a reaction gas containing HFC-143, hydrogen chloride and hydrogen fluoride by the production method of the present disclosure, HFC-143 can be obtained by various known separation methods. Hydrogen fluoride can also be recycled for the fluorination reaction. Further, the obtained HFC-143 can be used for various purposes after being subjected to a purification treatment as needed. For example, HFC-143 may be subjected to a hydrogen fluoride reaction to produce 1,2-difluoroethylene (HFO-1132). In this regard, the present disclosure comprises a step of subjecting 1,1,2-trifluoroethane (HFC-143) contained in the reaction gas obtained by the above-mentioned production method of the present disclosure to a hydrogen fluoride reaction. It also includes the invention of a method for producing 2-difluoroethylene (HFO-1132).

Although the embodiments of the present disclosure have been described above, the present disclosure is not limited to these examples, and it goes without saying that the present disclosure can be implemented in various forms without departing from the gist of the present disclosure.

Hereinafter, embodiments of the present disclosure will be described in more detail based on Examples. However, the present disclosure is not limited to the scope of the examples.

Example 1
A chromium oxide fluoride catalyst was prepared by the following procedure. First, chromium oxide represented by CrxOy was prepared according to the method described in JP-A-5-146680. Specifically, 10% aqueous ammonia is added to 765 g of a 775% aqueous solution of chromium nitrate, and the precipitate formed thereby is collected by filtration and washed, and then dried in air at 120 ° C. for 12 hours to obtain chromium hydroxide. Obtained. This chromium hydroxide was molded into pellets having a diameter of 3.0 mm and a height of 3.0 mm. The pellet was calcined in a nitrogen stream at 400 ° C. for 2 hours to obtain chromium oxide. The specific surface area of the obtained chromium oxide (according to the BET method) was about 200 m ² / g. Next, this chromium oxide was subjected to a fluorination treatment to obtain a chromium oxide fluoride catalyst. Specifically, a gas containing hydrogen fluoride is circulated through chromium oxide and heated while gradually raising the temperature from 200 to 360 ° C. After reaching 360 ° C., it is fluorinated with hydrogen fluoride for 2 hours to fluorinate. A chromium fluorinated catalyst was obtained.

12 g of the obtained chromium oxide fluoride catalyst was filled in a tubular Hastelloy reactor having an inner diameter of 15 mm and a length of 1 m.

This reaction tube is maintained at 150 ° C. under atmospheric pressure (0.0 MPaG), and anhydrous hydrogen fluoride (HF) gas is supplied to the reactor at a flow rate of 118 mL / min (flow rate at 0 ° C., 0.0 MPaG). It was maintained for 1 hour. Then, CHCl ₂ CH ₂ Cl (HCC-140) was supplied at a flow rate of 2.4 mL / min (gas flow rate at 0 ° C. and 0.0 MPaG). At this time, the molar ratio of HF: HCC-140 was 50: 1, and the contact time W / Fo was 6 g · sec / cc.

1.5 hours after the start of the reaction, the conversion of HCC-140 was 56.4% and the selectivity of HFC-143 was 0.4%.

Example 2
HFC-143 was synthesized in the same manner as in Example 1 except that the reaction temperature was set to 240 ° C.

2.5 hours after the start of the reaction, the conversion of HCC-140 was 99.8% and the selectivity of HFC-143 was 2.4%.

Example 3
HFC-143 was synthesized in the same manner as in Example 1 except that the reaction temperature was set to 280 ° C.

2.5 hours after the start of the reaction, the conversion of HCC-140 was 100% and the selectivity of HFC-143 was 6.5%.

Example 4
HFC-143 was synthesized in the same manner as in Example 1 except that the reaction temperature was set to 330 ° C.

1.5 hours after the start of the reaction, the conversion rate of HCC-140 was 100%, and the selectivity of HFC-143 was 4.1%.

Example 5
Anhydrous hydrogen fluoride (HF) gas was supplied to the reactor at a flow rate of 57.4 mL / min (flow rate at 0 ° C. and 0.0 MPaG), and the reaction temperature was set to 200 ° C. in the same manner as in Example 1. HFC-143 was synthesized. At this time, the molar ratio of HF: HCC-140 was 24.3: 1, and the contact time W / Fo was 12 g · sec / cc.

Two hours after the start of the reaction, the conversion of HCC-140 was 98.3% and the selectivity of HFC-143 was 0.1%.

Example 6
HFC-143 was synthesized in the same manner as in Example 5 except that the reaction temperature was set to 240 ° C.

Three hours after the start of the reaction, the conversion of HCC-140 was 100% and the selectivity of HFC-143 was 1.9%.

Example 7
HFC-143 was synthesized in the same manner as in Example 5 except that the reaction temperature was set to 280 ° C.

Two hours after the start of the reaction, the conversion rate of HCC-140 was 100%, and the selectivity of HFC-143 was 2.7%.

Example 8
Anhydrous hydrogen fluoride (HF) gas was supplied to the reactor at a flow rate of 35 mL / min (flow rate at 0 ° C. and 0.0 MPaG), and the reaction temperature was set to 280 ° C. in the same manner as in Example 1 HFC. -143 was synthesized. At this time, the molar ratio of HF: HCC-140 was 15: 1, and the contact time W / Fo was 19 g · sec / cc.

Two hours after the start of the reaction, the conversion rate of HCC-140 was 100%, and the selectivity of HFC-143 was 1.4%.

From the results of Example 8, since the yield of HFC-143 decreased by setting the molar ratio low, the molar ratio of HFC-143 was set to 20 or more, preferably 40 or more (particularly over 40). It can be seen that the yield is improved.

Example 9
HFC-143 was synthesized in the same manner as in Example 8 except that the reaction temperature was set to 365 ° C.

Two hours after the start of the reaction, the conversion of HCC-140 was 100% and the selectivity of HFC-143 was 0.27%.

Example 10
12 g of the chromium oxide fluoride catalyst prepared in Example 1 was filled in a tubular Hastelloy reactor having an inner diameter of 15 mm and a length of 1 m.

This reaction tube is maintained at 240 ° C. under atmospheric pressure (0.0 MPaG), and anhydrous hydrogen fluoride (HF) gas is supplied to the reactor at a flow rate of 63 mL / min (flow rate at 0 ° C., 0.0 MPaG). It was maintained for 1 hour. Then, CHClCHCl (HCO-1130) was supplied at a flow rate of 3 mL / min (gas flow rate at 0 ° C., 0.0 MPaG). At this time, the molar ratio of HF: HCO-1130 was 21: 1, and the contact time W / Fo was 11 g · sec / cc.

19 hours after the start of the reaction, the conversion of HCO-1130 was 29% and the selectivity of HFC-143 was 6.8%.

Example 11
Anhydrous hydrogen fluoride (HF) gas at a flow rate of 61.9 mL / min (flow rate at 0 ° C., 0.0 MPaG) and HCO-1130 at a flow rate of 4.1 mL / min (gas flow rate at 0 ° C., 0.0 MPaG). HFC-143 was synthesized in the same manner as in Example 10 except that each was supplied to the reactor. At this time, the molar ratio of HF: HCO-1130 was 15: 1, and the contact time W / Fo was 11 g · sec / cc.

Two hours after the start of the reaction, the conversion of HCO-1130 was 25.5% and the selectivity of HFC-143 was 3.3%.

Example 12
Anhydrous hydrogen fluoride (HF) gas at a flow rate of 64.7 mL / min (flow rate at 0 ° C., 0.0 MPaG) and HCO-1130 at a flow rate of 1.3 mL / min (gas flow rate at 0 ° C., 0.0 MPaG). HFC-143 was synthesized in the same manner as in Example 10 except that each was supplied to the reactor. At this time, the molar ratio of HF: HCO-1130 was 50: 1, and the contact time W / Fo was 11 g · sec / cc.

Two hours after the start of the reaction, the conversion of HCO-1130 was 63.5% and the selectivity of HFC-143 was 14.6%.

Comparing the results of Example 11 with the results of Examples 10 and 12, the yield of HFC-143 decreased due to the low molar ratio, so the molar ratio was 20 or more, preferably 40. It can be seen that the yield of HFC-143 is improved by setting the above (particularly over 40).

Example 13
Anhydrous hydrogen fluoride (HF) gas at a flow rate of 150 mL / min (flow rate at 0 ° C., 0.0 MPaG) and HCO-1130 at a flow rate of 3 mL / min (gas flow rate at 0 ° C., 0.0 MPaG) in the reactor. HFC-143 was synthesized in the same manner as in Example 10 except that the reaction pressure was 0.6 MPaG and the reaction temperature was 200 ° C. At this time, the molar ratio of HF: HCO-1130 was 50: 1, and the contact time W / Fo was 4.7 g · sec / cc.

Two hours after the start of the reaction, the conversion of HCO-1130 was 40% and the selectivity of HFC-143 was 5.9%.

Example 14
HFC-143 was synthesized in the same manner as in Example 13 except that the reaction pressure was 0.0 MPaG.

Two hours after the start of the reaction, the conversion of HCO-1130 was 25.4% and the selectivity of HFC-143 was 7.4%.

From the comparison between the result of Example 13 and the result of Example 14, it can be seen that the conversion rate can be greatly improved by increasing the pressure to 0.6 MPaG.

Example 15
The conditions shown in Example 14 were accompanied by 1% O ₂ with respect to the total flow rate.

Fifteen hours after the start of the reaction, the conversion of HCO-1130 was 44.2% and the selectivity of HFC-143 was 17.8%.

Example 16
HFC-143 was synthesized in the same manner as in Example 15 except that the reaction temperature was set to 260 ° C.

Two hours after the start of the reaction, the conversion of HCO-1130 was 54% and the selectivity of HFC-143 was 17.5%.

Example 17
HFC-143 was synthesized in the same manner as in Example 15 except that the reaction temperature was set to 280 ° C.

Two hours after the start of the reaction, the conversion of HCO-1130 was 55.4% and the selectivity of HFC-143 was 18.2%.

From the comparison between the results of Example 14 and the results of Examples 15 to 17, it can be seen that the addition of oxygen can improve not only the conversion rate but also the selectivity of HFC-143.

Claims (11)

A method for producing 1,1,2-trifluoroethane (HFC-143).
1,1,2-Trichloroethane (HCC-140), 1,2-dichloro-1-fluoroethane (HCFC-141), 1,1-dichloro-2-fluoroethane (HCFC-141a), (E, Z) At least one selected from the group consisting of -1,2-dichloroethylene (HCO-1130 (E, Z)) and (E, Z) -1-chloro-2-fluoroethylene (HCFO-1131 (E, Z)). A method for producing HFC-143, which comprises a step of carrying out one or more fluorination reactions by contacting the chlorine-containing compound of HFC with hydrogen fluoride to obtain a reaction gas containing HFC-143, hydrogen chloride and hydrogen fluoride. The production method according to claim 1, wherein the fluorination reaction is carried out under a pressure condition of 0 to 2 MPaG. The production method according to claim 1 or 2, wherein the fluorination reaction is carried out in the gas phase in the presence of a catalyst. The production method according to claim 3, wherein the fluorination reaction is carried out under temperature conditions of 150 to 600 ° C. The production method according to claim 3 or 4, wherein the contact time W / Fo between the chlorine-containing compound and the hydrogen fluoride in the fluorination reaction is 0.1 to 100 g · sec / cc. The production method according to any one of claims 1 to 5, wherein the molar ratio of hydrogen fluoride to the chlorine-containing compound in the fluorination reaction is 20 or more. The production method according to any one of claims 1 to 5, wherein the molar ratio of hydrogen fluoride to the chlorine-containing compound in the fluorination reaction exceeds 40. The production method according to any one of claims 3 to 7, wherein the catalyst is at least a chromium-based catalyst. The production method according to claim 1 or 2, wherein the fluorination reaction is carried out in a liquid phase in the presence of a catalyst. The production method according to claim 9, wherein the catalyst is at least a part of an antimony-based catalyst. A step of subjecting 1,1,2-trifluoroethane (HFC-143) contained in the reaction gas obtained by the production method according to any one of claims 1 to 10 to a hydrogen fluoride reaction. A method for producing 2-difluoroethylene (HFO-1132).